<?xml version="1.0" encoding="UTF-8"?><xml><records><record><source-app name="Biblio" version="7.x">Drupal-Biblio</source-app><ref-type>17</ref-type><contributors><authors><author><style face="normal" font="default" size="100%">Nair, Aathira</style></author><author><style face="normal" font="default" size="100%">Kenge, Nivedita</style></author><author><style face="normal" font="default" size="100%">Joshi, Kavita</style></author></authors></contributors><titles><title><style face="normal" font="default" size="100%">Role of facet in the competitive pathway of ethylene epoxidation</style></title><secondary-title><style face="normal" font="default" size="100%">Surface Science</style></secondary-title></titles><keywords><keyword><style  face="normal" font="default" size="100%">Ag(100)</style></keyword><keyword><style  face="normal" font="default" size="100%">Ag(111)</style></keyword><keyword><style  face="normal" font="default" size="100%">DFT</style></keyword><keyword><style  face="normal" font="default" size="100%">epoxidation</style></keyword><keyword><style  face="normal" font="default" size="100%">Ethylene Oxide (EtO)</style></keyword><keyword><style  face="normal" font="default" size="100%">OMC</style></keyword></keywords><dates><year><style  face="normal" font="default" size="100%">2022</style></year><pub-dates><date><style  face="normal" font="default" size="100%">FEB</style></date></pub-dates></dates><volume><style face="normal" font="default" size="100%">716</style></volume><pages><style face="normal" font="default" size="100%">121954</style></pages><language><style face="normal" font="default" size="100%">eng</style></language><abstract><style face="normal" font="default" size="100%">Ethylene epoxide (EtO) is used as raw material for a broad range of products from pharmaceuticals and plastics to paints and adhesives. Although the reaction of ethylene interacting with preadsorbed oxygen on Ag surface is known for decades, the underlying mechanism of EtO formation is not completely understood. Successful investigation of oxametallacycle (OMC) intermediate common to selective as well as non-selective pathways has ensured at least 50% selectivity. The current study brings out the electronic signatures of distinct conformers of OMC stabilised on two different facets of Ag viz. (100) and (111). There are subtle differences between OMC conformers observed on these two facets with near-eclipsed on Ag(100) and near-staggered on Ag(111). A detailed analysis of Ag-O, C-O, C-C, and Ag-C interactions along with projected Density of States (pDOS) and projected Crystal Orbital Hamilton Population (pCOHP) imply towards ring closure on Ag(100) and hydrogen transfer on Ag(111). Finally, our understanding based on electronic and structural signatures are backed up by activation barriers computed through NEB calculations. Activation barrier for EtO is lower on (100) as compared to (111) facet. Thus, our study sheds light on how these differences between OMC affect the selectivity towards EtO.</style></abstract><work-type><style face="normal" font="default" size="100%">Article</style></work-type><custom3><style face="normal" font="default" size="100%">Foreign</style></custom3><custom4><style face="normal" font="default" size="100%">1.942</style></custom4></record><record><source-app name="Biblio" version="7.x">Drupal-Biblio</source-app><ref-type>17</ref-type><contributors><authors><author><style face="normal" font="default" size="100%">Nair, Aathira</style></author><author><style face="normal" font="default" size="100%">Joshi, Kavita</style></author></authors></contributors><titles><title><style face="normal" font="default" size="100%">What leads to direct epoxidation? an exhaustive DFT investigation of electrophilic oxygen mediated epoxidation of ethylene on Ag(100)</style></title><secondary-title><style face="normal" font="default" size="100%">Computational Materials Science </style></secondary-title></titles><keywords><keyword><style  face="normal" font="default" size="100%">Ag(100)</style></keyword><keyword><style  face="normal" font="default" size="100%">DFT</style></keyword><keyword><style  face="normal" font="default" size="100%">Direct epoxidation</style></keyword><keyword><style  face="normal" font="default" size="100%">Electrophilic oxygen</style></keyword><keyword><style  face="normal" font="default" size="100%">Ethylene Oxide (EtO)</style></keyword><keyword><style  face="normal" font="default" size="100%">OMC</style></keyword></keywords><dates><year><style  face="normal" font="default" size="100%">2024</style></year><pub-dates><date><style  face="normal" font="default" size="100%">APR</style></date></pub-dates></dates><volume><style face="normal" font="default" size="100%">239</style></volume><language><style face="normal" font="default" size="100%">eng</style></language><abstract><style face="normal" font="default" size="100%">&lt;p&gt;
	Extensive research has contributed to a better understanding of the commercially important epoxidation reaction. Selectivity, a crucial aspect of this reaction, has received significant attention in both experimental and theoretical investigations. However, a consensus regarding the role of electrophilic oxygen in epoxidation is yet to be reached. The present study is a theoretical examination of the prerequisites necessary for direct epoxidation to occur on the Ag(100) surface, at varied monolayer concentrations. Additionally, the study investigates the characteristics of various oxygen species interacting with ethylene to promote the direct epoxidation pathway. Based on the effective charges and projected density of states (pDOS) analysis, three oxygen variants were identified on the Ag(100) surface: atomic oxygen, dissociatively adsorbed molecular oxygen, and O 3 . The investigation reveals that all oxygen species, despite their physical and electronic differences, are electrophilic and undergo direct epoxidation. This work provides insights into the complex nature of epoxidation reaction and discusses electronic factors influencing the selective oxidation route on different Ag-O complexes.&lt;/p&gt;
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	Foreign&lt;/p&gt;
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	3.3&lt;/p&gt;
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